CN110958862B - Water-resistant polymer-based dental articles - Google Patents

Abstract

A dental article, such as a tray appliance or a crown, includes a substrate comprising a polymeric material having a modulus of elasticity that decreases upon contact with water, and a water-resistant coating on the substrate, wherein the water-resistant coating comprises parylene. In some examples, the water-resistant coating may include one or more layers comprising parylene.

Description

Polymer-Based Water-Resistant Dental Products

technical field

The present disclosure relates to polymer-based dental articles, such as dental appliances.

Background technique

The field of orthodontics is concerned with supervising, guiding and straightening teeth towards their correct position in the mouth. Various orthodontic devices and treatments have been developed to address tooth alignment issues. Traditional methods generally involve applying force to move the teeth into the correct occlusal configuration or closure. One treatment modality involves the use of fixtures attached to the patient's teeth, and the use of archwires, applying gentle treatment forces, to move the teeth from out of place to in place. Such dental appliances remain in the patient's mouth and are regularly adjusted by the orthodontist to check the process and maintain proper pressure on the teeth until proper alignment is achieved.

Dental appliances and other dental articles have been prepared using polymer-based components. In some such examples, the polymer-based component may be relatively transparent or transparent to provide a less conspicuous appearance than metal, ceramic, or similar types of devices.

SUMMARY OF THE INVENTION

In some examples, the present disclosure describes a dental article comprising a substrate comprising a polymeric material, wherein the elastic modulus of the substrate decreases upon exposure to water, and a water-resistant coating on the substrate layer, wherein the water resistant coating comprises parylene.

In some examples, the present disclosure describes a dental article that includes a three-dimensionally printed polymeric substrate and a water-resistant coating applied on the substrate, wherein the water-resistant coating includes a parylene layer.

In some examples, the present disclosure describes a method comprising forming a substrate for a dental article, wherein the elastic modulus of the substrate decreases upon contact with water, and coating with a water-resistant coating comprising parylene layer coated substrate.

In some examples, the present disclosure describes a method comprising forming a model of a patient's dental anatomy, applying a first coating comprising parylene on the model, thermoforming a polymer on the first coating a sheet of material, trimming a sheet of polymeric material to form a polymer-based substrate, applying a second coating comprising parylene to the exposed surface of the polymer-based substrate, trimming the second coating To define a dental article, the dental article includes a polymer-based substrate, a first coating and a second coating, and the dental article is separated from the model.

The details of one or more examples are set forth in the accompanying drawings and the description below. Other features, objects and advantages of the present invention will be apparent from the detailed description and drawings, and from the claims.

Description of drawings

1 is a perspective view of an example dental article including a polymer-based substrate and a water-resistant coating comprising parylene.

2-4 are cross-sectional views of example dental articles that include a polymer-based substrate having a multi-layer, water-resistant coating comprising parylene.

5 is a flow diagram illustrating an example technique for forming a dental article including a polymer-based substrate and a water-resistant coating comprising parylene.

6 is an example flow diagram illustrating a technique for simultaneously forming a polymer-based substrate and applying a water-resistant coating comprising parylene on the polymer-based substrate.

7A-7G are schematic cross-sectional views of an example layer building method for forming a dental article encapsulated with a water-resistant coating comprising parylene.

Detailed ways

The present disclosure describes dental articles that include a polymer-based substrate and a water-resistant coating comprising parylene, and methods of making them. Such dental devices may include, for example, braces, crowns, night guards, retainers, implants, dentures, partials, temporary replacements, elastic bands, springs, spring appliances, polymeric arch wires and arcuate members, custom force members, accessories, brackets and other bonded appliances, trays for delivering therapeutic agents, and the like. This description focuses primarily on and describes dental appliances; however, many dental articles can be constructed using the components and techniques described herein. This disclosure is not intended to be limited to a particular type of dental article by focusing on the details of a dental brace.

The dental articles described herein can include a polymer-based substrate and a water-resistant coating comprising parylene on the substrate. In some examples, polymeric materials used to form substrates for such dental articles can exhibit several useful qualities, such as moldability, printability, stiffness, strength, durability, aesthetic color, or transparency , tactilely pleasing textures, etc. However, some polymeric materials used in such devices undergo softening or degradation of mechanical properties over time in the presence of water, such as reducing the elastic modulus of the substrate. For example, some polymeric materials can have relatively high elastic moduli due in part to hydrogen bonding between polymer chains. Exposure to water reduces or eliminates hydrogen bonds, which can reduce the elastic modulus of the polymeric material. This reduction results in softening of the substrate, which can make polymer-based substrates less suitable for use in certain types of devices, including, for example, braces or other dental articles for applying or retaining force to a patient's teeth. For example, braces can be used to apply mechanical force to a patient's teeth to move the teeth into a new alignment. In order to move the teeth, the dental appliance must apply a treatment force to the teeth that is greater than the threshold required to stimulate bone remodeling and corresponding movement of the teeth. When exposed to water, the reduced elastic modulus or restoring force may inhibit the ability of the tray appliance to apply or maintain this therapeutic force, thereby rendering the tray appliance ineffective, or at least in its ability to express prescribed movement of the teeth somewhat reduced.

Coating such polymer-based substrates with a water-resistant coating comprising parylene can significantly reduce the deleterious effects of exposing the polymer-based substrate to water, as well as impart other useful benefits to dental devices. In some examples, the water resistant coating can include a layer comprising parylene. The layer comprising parylene may be applied using chemical vapor deposition methods. Vapor deposition methods can result in layers with relatively high density (low porosity), which can contribute to the water resistance of the coating. Additionally or alternatively, vapor deposition methods can produce layers that substantially conform to the geometry of the substrate. For example, the layers may have substantially uniform thicknesses. This can facilitate the coating of polymer-based substrates, while also achieving the target geometry of the dental article, which can be important for dental devices such as braces, etc., where a fine fit can be used to achieve desired results with the device is important.

FIG. 1 is a perspective view of an example dental article 10 that includes a polymer-based substrate 12 and a water-resistant coating 14 on the polymer-based substrate 12 that includes parylene. In the example of FIG. 1, the dental article 10 includes a dental appliance. However, the dental article 10 is not necessarily limited to braces. In other examples, the dental article 10 may include other polymer-based devices for use in dental procedures, including but not limited to crowns, night guards, retainers, implants, dentures, parts, temporary replacements, elastics Straps, springs, spring appliances, polymeric archwires and arcuate members, custom force members, accessories, brackets and other bonding implements, trays for delivering therapeutic agents, and the like.

In some examples, the polymer-based substrate 12 may comprise a biocompatible polymer material. Depending on the particular application used for the dental article 10, in some implementations, the polymer-based substrate 12 can have a modulus of elasticity greater than about 100 MPa, such as between about 300 MPa and about 5 MPa. However, as discussed above, the elastic modulus of such polymers may decrease upon exposure to water. In addition, water contact can cause stress relaxation of the deformed polymer, thereby reducing the restoring force applied to the teeth. In some examples, the relatively high elastic modulus of the polymer-based substrate 12 may allow the dental article 10 to exhibit sufficient stiffness even when the polymer-based substrate 12 is relatively thin. For example, when the dental article 10 is a dental appliance, the stiffness of the polymer-based substrate 12 may allow the appliance to apply a therapeutic force to actively compress the patient's teeth and guide the teeth into a new alignment. In order to cause tooth movement, the treatment force must generally be above a threshold. This threshold may be somewhat generalized to fit a typical population of patients, or it may be customized based on a number of factors, including systolic blood pressure, bone density, immune system health, use of anti-inflammatory drugs, and the like. Once the braces are removed, the teeth will remain in their original position, or at least partially return to their previous position. Thus, in some examples, by formulating the polymer-based substrate 12 to have and maintain a modulus of elasticity greater than about 300 MPa, the polymer-based substrate 12 can be maintained even when the thickness of the article remains relatively thin (eg, about 300 MPa). Micrometers (μm) to about 1000 μm) can also apply the desired treatment force to the teeth.

Additionally or alternatively, by formulating the polymer-based substrate 12 to define a modulus of elasticity of less than about 5 GPa, the polymer-based substrate 12 may still retain some flexibility to allow the dental device 10 to have when desired some degree of flexibility. In the example of a dental appliance, the flexibility of the polymer-based substrate 12 may allow the dental article 10 to be advanced over the contours of the patient's teeth to allow insertion and/or removal of the dental article 10 as needed. In some examples, the elastic modulus of the material can be measured according to ASTM D638.

In some examples, the polymer-based substrate 12 may comprise (meth)acrylate polymers, epoxies, siloxanes, polyesters, polyurethanes, thiol polymers, and the like. Suitable acrylate polymers may include urethane (meth)acrylate polymers, polyalkylene oxide di(meth)acrylates, alkanediol di(meth)acrylates, aliphatic (meth)acrylates Acrylates, silicone (meth)acrylates, etc. In some examples, the polymer-based substrate 12 may comprise a urethane (meth)acrylate polymer comprising alkyl, polyalkylene, polyalkylene oxide, aryl, polycarbonate , polyester, polyamide, and combinations thereof. Exemplary urethane (meth)acrylate polymers suitable for use as polymer-based substrate 12 are described in co-pending US Provisional Patent Application Serial No. 62/536,568 to Parkar et al., entitled Photopolymerizable Compositions Including a Urethane Oligomer and a Reactive Diluent, Articles, and Methods, the contents of which are incorporated by reference in their entirety This article. Such urethane (meth)acrylate polymers are particularly useful due to their mechanical properties at body temperature or 3D printing capabilities. However, urethane (meth)acrylate polymers are hydrophilic, and the mechanical properties of urethane (meth)acrylate polymers can degrade in a water-rich environment, such as in a patient's mouth. For example, exposure to water can cause the elastic modulus or stress relaxation of the urethane (meth)acrylate polymer to decrease, eg, due to the loss of secondary interactions such as hydrogen bonding. Thus, in applications where the dental article 10 is used to apply force to a patient's teeth, the dental article 10 may not function properly for a period of time. In such examples, application of the water-resistant coating 14 with parylene can significantly reduce or prevent hydrolytic degradation of the urethane (meth)acrylate substrate.

In some examples, the polymer-based substrate 12 may include a polyethylene terephthalate-based polymer, such as polyethylene terephthalate glycol (PETG). PETG is a thermoplastic polymer that exhibits a sufficient modulus of elasticity (eg, about 1.95 GPa) at room temperature. PETG can have high tensile strength, high impact strength, high flexural strength, good heat resistance and good printability.

The polymer-based substrate 12 may be formed into a desired shape using any suitable technique. In some examples, the polymer-based substrate 12 may be formed into the shape of the patient's teeth using thermoforming molding methods. For example, a mold plug or male model of at least a portion of a patient's dental anatomy may be formed using a suitable technique, such as by 3D printing, milling, cast impression casting, or setting segmented teeth in wax. A sheet of material used to form the polymer-based substrate 12 may be heated to its glass transition temperature, draped over the dental model and subjected to an air pressure differential such that a greater proportion of the material is applied to the outer surface of the sheet adjacent the inner surface of the model. higher pressure. Note that this pressure difference is called "vacuum" if the pressure of the adjacent model is lower than the ambient air pressure, and "positive pressure" if the pressure applied to the outer surface is higher than the ambient air pressure. The pressure differential conforms the sheet to the surface of the dental model and maintains shape by maintaining the pressure differential until the sheet cools below its glass transition temperature.

In other examples, three-dimensional printing or additive manufacturing may be used to form the polymer-based substrate 12 . For example, a digital three-dimensional representation of a patient's teeth can be generated using, for example, an intraoral scanner. The polymer-based substrate 12 can then be prepared directly using a three-dimensional printer based on the digital representation of the teeth.

However, as discussed above, some polymers used to form polymer-based substrate 12 may be suitable for three-dimensional additive manufacturing, but may absorb water or be softened in the presence of water, which may result in such polymers being less Suitable for certain types of dental applications (eg, braces). Additionally, 3D printing methods add materials to parts on a layer-by-layer or volume-by-volume basis. Such construction techniques can produce textured surfaces marked by contour lines or "steps" (also known as aliasing effects), which are less than ideal in oral applications due to poor sensory perception. Additionally, polymer-based substrates (especially transparent polymers) formed using 3D printing devices can scatter light due to the stepped or textured structures created by the layer-by-layer or volume-by-volume build process. This results in a reduction in the optical clarity of the polymer-based substrate 12 . In applications where aesthetics and transparency are important, such as in dental braces, such three-dimensional printing-related deficiencies make such construction techniques less than ideal due to poor visual and tactile properties.

Other undesirable effects from aliasing or surface roughness may include biofilm formation and increased friction or interference with opposing surfaces in the dentition. Oral biofilms include bacterial cultures that can lead to acid production, odor, and stone accumulation. The interior corners created at the boundaries of the material layers during the manufacturing process can serve as a shelter for bacterial cultures, protecting them from saliva flow and the wiping action of the tongue and oral mucosa. In some examples, similar effects may result from finer levels of texture created at the exposure boundaries during the photopolymerization process used to form polymer-based substrate 12 . Such textures may include microscopic textures (eg, textures less than about 20 μm in size) that are characterized on a much smaller scale than pixels or print layers. Therefore, biofilm adhesion can occur on the surface of the appliance if it is not polished to a high gloss or protected with a glossy coating.

The dental article 10 may include a water resistant coating 14 that may address some or all of these undesirable effects. For example, the water-resistant coating 14 may improve the stability of the dental article 10 when exposed to water. In such examples, the water-resistant coating 14 may act as a barrier to water, reducing or substantially preventing the entry of water into the polymer-based substrate 12, thereby allowing the polymer-based substrate 12 to substantially retain its mechanical properties. Additionally, in some examples, the barrier properties of parylene within the water-resistant coating 14 may also reduce the risk of trace amounts of free monomers, initiators, or other molecules diffusing from the polymer-based substrate 12 into the oral environment. Transmittance.

Additionally or alternatively, the water resistant coating 14 may improve the visual or tactile properties of the dental article 10 . For example, as described further below, parylene can be deposited by chemical vapor deposition using paraxylene gas for polymerization. Due to the small size of the paraxylene molecule and the deposition method, parylene can be deposited as a relatively dense and water resistant layer, especially compared to other polymer coatings deposited using liquid-based coating methods. In some examples, the layer comprising parylene that forms the water-resistant coating 14 may define a porosity of less than about 5%. Porosity is defined as the volume of pores divided by the total volume of the corresponding layers of the water-resistant coating 14, and can be measured using optical microscopy, mercury intrusion, and the like.

Additionally or alternatively, applying the water-resistant coating 14 comprising parylene can reduce the roughness of the outer surface of the polymer-based substrate 12 . For example, where three-dimensional printing is used to produce the polymer-based substrate 12, the water-resistant coating 14 may coat the surface of the polymer-based substrate 12 as well as the smooth aliasing effect or general surface texture produced by the printing method . Additionally or alternatively, the polymer-based substrate 12 may define a first surface roughness due to process formation techniques of the polymer-based substrate 12, such as three-dimensional printing or other techniques. Due to the vapor deposition method of forming the water-resistant coating 14 comprising parylene, the parylene can smooth the surface of the polymer-based substrate 12 such that the outer surface of the water-resistant coating 14 is less defined than the polymer-based substrate A second surface roughness of 12. In general, by reducing the overall surface roughness or the presence of surface texture of the dental article 10, the water-resistant coating 14 comprising parylene can also inhibit the Biofilm formation. Additionally or alternatively, the reduced surface roughness due to the presence of the water-resistant coating 14 comprising parylene may also reduce dental The coefficient of friction of the article 10.

In some examples, the water-resistant coating 14 comprising parylene can provide a glossy surface. For example, parylene may be applied using chemical vapor deposition (CVD) methods, such as polymer vapor deposition (PVD) methods, wherein parylene is formed from a single monomer directly on the surface of polymer-based substrate 12 molecular formation. These molecules are supplied in gaseous form and condense as polymers on the surface of the substrate, allowing their deposition in the smallest microscopic cavities. As more and more molecules integrate with the surface, the coating becomes thicker, eventually filling and smoothing over these microscopic cavities. In addition to bonding to the substrate, the ability of parylene to fill microscopic cavities provides excellent mechanical interlocking. The result is a strong interface that resists delamination.

By smoothing the outer surface of the dental article 10, the article 10 can have an improved sensory feel in the patient's mouth. Additionally, smoothing the outer surface of the dental article 10 with the water resistant coating 14 may improve the resulting article 10 in some examples where the polymer-based substrate 12 is transparent due to the deposition of parylene as a clear coat Transparency and overall visual aesthetics. Additionally, a more linear path for light transmission may be established through parylene, thereby improving the optical clarity of the dental article 10 . In contrast, coatings applied as high viscosity liquid resins and subsequently polymerized can suffer from incomplete penetration of microscopic cavities in the surface.

In addition, in some examples, the water-resistant coating 14 comprising parylene may also be effective in reducing the adhesion and/or penetration of stains such as curry, mustard, wine, coffee, etc., present in the oral cavity, to prevent Provides improved visual aesthetics during its service life.

(用氟取代N二聚物的α氢原子)、可得自特种涂料系统公司(Specialty Coating Systems)的SCS

抗微生物聚对二甲苯技术、可得自印第安纳州印第安纳波利斯的特种涂料系统公司(Specialty Coating Systems,Indianapolis,IN)的聚对二甲苯

或它们的组合)。在一些示例中，包含聚对二甲苯的层可使用自引发的化学气相沉积方法沉积，其中对二甲苯二聚体(例如，为制备聚对二甲苯-C而开发的[2.2]对环芳烷)是起始组分。例如，基于聚合物的基材12可被定位在真空沉积室中，该真空沉积室被抽空至约0.1托(约13.33帕斯卡)的数量级的压力，从而导致沉积室中的气体分子的平均自由路径为0.1cm的数量级。可将固态或气态的对二甲苯二聚体加热至使对二甲苯二聚体分解成单体对二甲苯气体的温度。由于在分解过程中不形成侧分子，所得的单体对二甲苯气体将为基本上纯的。可将单体气体引入到包含基于聚合物的基材12的真空沉积室中。然后可将单体气体沉积在基于聚合物的基材12上。由于气态对二甲苯单体的平均自由路径为0.1cm的数量级，因此沉积过程可为非视线过程，并且聚对二甲苯可沉积在基于聚合物的基材12的全部或几乎所有表面上。因此，在一些示例中，聚对二甲苯可基本上包封(例如，完全包封或几乎完全包封)基于聚合物的基材12。The water-resistant coating 14 may include a layer comprising parylene (eg, parylene-C (polychloroparaxylylene), parylene-D (polydichloroparaxylylene) , Parylene-F (polytetrafluoroparaxylylene), Parylene-N (Parylene), available from Specialty Coating Systems, Indianapolis , IN) parylene

(Alpha hydrogen atoms of N dimer replaced with fluorine), SCS available from Specialty Coating Systems

Antimicrobial Parylene Technology, Parylene available from Specialty Coating Systems, Indianapolis, IN

or their combination). In some examples, layers comprising parylene can be deposited using a self-initiated chemical vapor deposition method in which a paraxylene dimer (eg, [2.2]paracyclic aromatics developed for the production of parylene-C) alkane) is the starting component. For example, polymer-based substrate 12 may be positioned in a vacuum deposition chamber that is evacuated to a pressure on the order of about 0.1 Torr (about 13.33 Pascals), resulting in a mean free path for gas molecules in the deposition chamber is of the order of 0.1 cm. The solid or gaseous para-xylene dimer can be heated to a temperature at which the para-xylene dimer is decomposed into monomeric para-xylene gas. Since no side molecules are formed during decomposition, the resulting monomeric paraxylene gas will be substantially pure. The monomer gas can be introduced into the vacuum deposition chamber containing the polymer-based substrate 12 . The monomer gas can then be deposited on the polymer-based substrate 12 . Since the mean free path of gaseous paraxylene monomer is on the order of 0.1 cm, the deposition process can be a non-line-of-sight process, and parylene can be deposited on all or nearly all surfaces of polymer-based substrate 12 . Thus, in some examples, the parylene can substantially encapsulate (eg, fully or nearly fully encapsulate) the polymer-based substrate 12 .

In some examples, because the parylene is deposited via vapor deposition rather than liquid deposition methods, the parylene does not pool, bridge, or exhibit meniscus characteristics and defects during the deposition process. Thus, parylene can be applied to the polymer-based substrate 12 as a relatively thin and substantially uniform water-resistant coating 14 . For example, the thickness and uniformity of a liquid-based coating can be related to viscosity, operating temperature and humidity, and method of application (eg, spraying or dipping). In some examples, the thickness of the coating applied using liquid-based coating techniques can vary by up to ±50% of the target final thickness of the liquid coating. This problem can be exacerbated when coating complex geometries, such as orthodontic appliances that contain many areas of high and complex curvature. In contrast, the thickness of a layer comprising parylene deposited using vapor deposition methods can be a function of the amount of vaporized dimer and the dwell time of the chamber. In some examples, the thickness of the layer comprising parylene may be controlled to a tolerance of about ±5% of the target thickness.

The improved tolerances associated with the thickness of the water resistant coating 14 may be useful in certain orthodontic applications, such as braces, where braces are designed to move a patient's teeth in fractions of a millimeter at a time. In contrast, liquid-based coatings (eg, those produced by spray or dip deposition techniques) can create uneven thickness and high spots in the coating, which can lead to twisted spots or uneven spots on the patient's teeth. Anticipated pressure points, resulting in misalignment or increased discomfort. The uniformity of the water-resistant coating 14 can improve the abrasion resistance, accuracy, and effectiveness of the dental article 10 .

In some examples, the final thickness of the parylene-containing water-resistant coating 14 may be at least about 5 μm, at least about 15 μm, at least about 25 μm, at least about 50 μm, at least about 100 μm, or at least about 150 μm. In some examples, the final thickness of the parylene-containing water-resistant coating 14 may be less than about 2 mm, less than about 1 mm, less than about 250 μm, less than about 100 μm, or less than about 50 μm. However, in other examples, the thickness of the water-resistant coating 14 comprising parylene may be greater than about 50 μm, such as at most about 5 mm. In some examples, the final thickness of the parylene layer within the water-resistant coating 14 may be greater than about 25 μm and less than about 200 μm. Making the parylene layer larger than at least about 25 μm can help reduce the aliasing effects described above.

In some such examples, the mechanical properties of the dental article 10 having a very thick parylene layer may be primarily attributable to the parylene coating rather than the underlying substrate. Thick parylene layers can provide desirable and stable elastic modulus, high fracture toughness, low creep, high transparency, high stain resistance, and the like. In some examples, water-resistant coating 14 includes a layer comprising parylene that defines a thickness greater than the thickness of polymer-based substrate 12 measured in a direction normal to the surface of polymer-based substrate 12 .

Additionally, in contrast to other types of water-resistant coatings, the deposition reaction of paraxylene to form parylene is self-initiated and self-propagating, and does not require the presence of catalysts, solvents, or other foreign substances to deposit the coating. Accordingly, the water-resistant coating 14 including a layer comprising parylene can be of high purity, resulting in less or substantially unnecessary processing aids (eg, catalysts and solvents) as residual components within the dental article 10 . . In addition, since the decomposition of the paraxylene dimer and the paraxylene monomer gas is a cleaning reaction that does not produce any by-products, the purity of the water-resistant coating 14 can be further controlled based on the purity of the paraxylene dimer raw material. Parylene also has excellent biocompatibility.

In some examples, the dental article 10 may also include a desiccant (eg, a hygroscopic agent) in or on the polymer-based substrate 12 . A desiccant may be used in conjunction with the water-resistant coating 14 to minimize the effect of water on the mechanical properties (eg, elastic modulus) of the polymer-based substrate 12 . For example, the desiccant can help sequester any residual moisture in the polymer-based substrate 12 prior to application of the water-resistant coating 14 . Additionally or alternatively, the desiccant may sequester any moisture that penetrates the water-resistant coating 14 to prevent moisture from degrading the mechanical properties of the polymer-based substrate 12 .

In some examples, the desiccant may include silica gel, sodium aluminosilicate, zeolite, hydrophilic polymers, clays, and the like. The desiccant may be added in any suitable amount so as not to significantly alter the underlying mechanical properties of the polymer-based substrate 12 . In some examples, a suitable amount may include about 5% by weight of the polymer-based substrate 12 .

In other examples, the desiccant may be deposited on the polymer-based substrate 12 prior to applying the water-resistant coating 14 . In some such examples, the desiccant may be incorporated into or onto the polymer-based substrate 12 in selected areas of the dental article 10 where the mechanical properties of the device are less critical (eg, in the palatal region) and Not in or on other areas of the substrate.

In some examples, the water-resistant coating 14 may include multiple layers, including at least one layer including parylene, but not a single layer including parylene. For example, FIG. 2 shows a cross-sectional view of an example dental article 20 that includes a polymer-based substrate 12 and a multi-layer water-resistant coating 22 . Aside from the differences described herein, the article 20 including the polymer-based substrate 12 may be substantially the same as the article 10 of FIG. 1 .

The water resistant coating 22 may include multiple layers, such as a first layer 24 comprising parylene on the polymer-based substrate 12, an intermediate layer 26 on the first layer 24 comprising an inorganic material or a polymer hard coat and an optional second layer 28 comprising parylene on the intermediate layer 26 .

The first layer 24 and the second layer 28 may each define a layer thickness between about 5 μm and about 50 μm, such as between about 5 μm and about 25 μm. Each of the first layer 24 and the second layer 28 may be similar or substantially the same as the parylene-containing layers described above with respect to the water-resistant coating 14 . In some examples, first layer 24 and second layer 28 may work together to reduce or substantially prevent water from entering water-resistant coating 22 and water absorption by polymer-based substrate 12 .

An intermediate layer 26 may be deposited between the first layer 24 and the second layer 28 . The intermediate layer 26 may comprise an inorganic material, such as a metal, metal alloy, metal oxide, ceramic, glass, or crystalline mineral, which improves the performance of the dental article 20 compared to an article comprising a water-resistant coating comprising only a layer comprising parylene. Durability and wear resistance properties.

For example, while the first layer 24 and the second layer 28 may provide adequate water barrier properties, parylene may have relatively low abrasion resistance. In some such examples, the parylene-containing layer may become worn through repeated contact or friction with other objects, such as teeth, food, and the like. While lower wear characteristics may be acceptable for certain dental applications (eg, removable braces), such wear characteristics may be relatively high for applications where the dental article is fixed or relatively permanent. Not acceptable. Such dental applications requiring an increased level of wear resistance may include crowns, bridges, dentures, occlusal splints, orthodontic brackets, etc., where the dental article 20 remains fixed in the patient's mouth and is in repeated contact with teeth, food, etc. ( e.g. chewing, grinding). In such applications, an intermediate layer 26 may be included in the dental article 20 to increase the durability and wear resistance of the article 20 as compared to an article having a water resistant layer that includes only a single layer with parylene. Additionally or alternatively, intermediate layer 26 may include a material (eg, metal oxide) that may provide article 20 with additional barrier properties (eg, water and/or antimicrobial barrier properties).

Example inorganic materials that may be used to form intermediate layer 26 include, for example, metals (eg, gold, silver, aluminum, copper, indium, or titanium); metal alloys; metal oxides, glasses, or ceramics (eg, silicon dioxide, aluminum oxide, or oxides) zirconium); diamond-like carbon; metal salts; etc. Metal salts such as chlorides, fluorides, sulfates and carbonates can be formed by subsequent contact with acids or gases containing these ions. In some cases, applying a positive charge to the metal layer can be beneficial for attracting the negative ions required to form the salt. In some examples, the intermediate layer 26 itself may be a multi-layer comprising layers of different inorganic materials.

The intermediate layer 26 may include an elemental metal layer and an oxide layer formed by exposing the elemental metal to the atmosphere or an oxygen-enriched gas environment. In some examples, as described further below, metal oxides can be used to provide antimicrobial or antibacterial properties to reduce or substantially prevent at least one of the undesired consequences of microbial contamination, such as, for example, microbial contamination that can occur through surfaces Or unwanted odor, flavor or discoloration caused by biofilms formed on the surface of article 20 .

Any suitable biocompatible metal oxide may be included in the intermediate layer 26, including, for example, at least one of silver oxide, zinc oxide, copper oxide, titanium oxide, aluminum oxide, and mixtures and alloys thereof, such as silver copper zinc Oxides of alloys (eg, _AgCuZnOx ), silver-doped zinc oxide, silver-doped aluminum oxide, silver-doped titanium oxide, and aluminum-doped zinc oxide. In some examples, in addition to metal oxides, intermediate layer 26 may optionally include additional metal compounds, such as silver chloride, silver bromide, silver iodide, silver fluoride, copper halide, zinc halide, and combinations thereof. Additional examples regarding the properties of metal oxide-incorporated layers are described in US Provisional Patent Application Serial No. 62/685,773, which is incorporated herein by reference in its entirety.

In other examples, the intermediate layer 26 may include a polymer hard coat. As used herein, "polymer hard coat" may be used to describe a polymer-based coating that has higher abrasive wear resistance than a parylene layer of the same thickness. In some examples, abrasive wear resistance properties can be measured by rubbing the dental replacement material against the surface of a corresponding layer of coating material and assessing damage to the layer after a simulated two-week wear. The interlayer 26 comprising the polymeric hard coat may improve the durability and wear resistance properties of the dental article 20 as compared to an article comprising a water resistant coating comprising only a layer comprising parylene. Additionally or alternatively, the polymeric hard coat can improve the abrasive resistance of the dental article 20 .

Exemplary materials suitable for use in polymeric hard coats may include, for example, crosslinkable matrix monomers, oligomers, or polymers with one or more functionalized inorganic fillers. Inorganic fillers can help improve the abrasion resistance of the resulting layer. In some examples, polymeric hard coats can be prepared as one-component mixtures, multi-component curable formulations, dispersions, and the like. Preferred polymeric hard coats can be relatively transparent/translucent, smooth, provide strong adhesion to the first layer 24, have some flexibility during use to minimize cracking, stain resistance, have greater than poly Grinding resistance to xylene or a combination thereof. Example polymeric hard coats may include 3M 906 abrasion resistant hard coats available from 3M Corporation, St. Paul, MN, USA or as described in US Patent Publication 2015-0132583 Hardcoat, which is incorporated herein by reference in its entirety.

其包含聚对二甲苯-C和被设计成在黑光下发荧光的特殊化合物。In some examples, the intermediate layer 26 may optionally contain dyes or pigments to provide a desired color, which may be, for example, decorative or selected to improve the appearance of the patient's teeth. In addition to the inorganic materials or polymer hard coats described above, dyes or pigments may be added. Additionally or alternatively, the first layer 24 or the second layer 28 may be configured to exhibit certain optical properties. For example, the first layer 24 or the second layer 28 may comprise parylene

It contains parylene-C and a special compound designed to fluoresce under black light.

The intermediate layer 26 may be deposited on the first layer 24 using any suitable technique including, for example, chemical vapor deposition, plasma chemical vapor deposition, evaporative deposition, sputtering, atomic layer deposition, electroless plating (eg, chemical or automated deposition). catalytic plating), electroplating (eg, after the first conductive layer has been deposited on the polymer-based substrate 12), spray coating, dip coating, and the like. In some examples, the thickness of the intermediate layer 26 is between about 0.1 microns and about 5 microns.

Although the dental article 20 is shown as having a first layer 24 and a second layer 28 each having parylene, in other examples, only one of the first layer 24 or the second layer 28 may be present. For example, FIG. 3 is a schematic cross-sectional view of an example dental article 30 that includes a polymer-based substrate 12 having a multi-layer water-resistant coating 32 comprising parylene. The multi-layer water resistant coating 32 may include a first layer 24 having parylene on the polymer-based substrate 12 and an outer layer 34 on the first layer 24 . Outer layer 34 may include a layer of inorganic material, a layer of polymeric hardcoat, or a combination thereof (eg, a layer of polymeric hardcoat over a layer of inorganic material). In some examples, outer layer 34 may be substantially the same (eg, the same or nearly the same) as intermediate layer 26 and may include inorganic materials, polymeric hard coats, and/or layer additives as described above with respect to intermediate layer 26 .

In some examples, the first layer 24 of the multi-layer water resistant coating 32 may help smoothen the outer surface of the polymer-based substrate 12 and reduce the transmission rate of water vapor or other contaminants through the first layer 24 . In some examples, the outer layer 34 may be relatively thin (eg, on the order of tens of nanometers) while still providing the dental article 10 with increased abrasion or wear resistance. Additionally or alternatively, the outer layer 34 may provide a more continuous coating due to the smoothing effect of the first layer 26 .

In some examples, outer layer 34 may include one or more metal oxides similar or substantially the same as those described above with respect to intermediate layer 26 . In some examples, metal oxides may be used within outer layer 34 to provide at least one of antimicrobial, antibacterial, or anti-biofilm properties for extended periods of time to reduce or substantially prevent the undesired consequences of microbial contamination At least one of the undesirable odors, flavors, or discolorations that may be caused by microbial contamination of the surface or by biofilms formed on the surface of the article 30, such as, for example, for example. In some examples, an antimicrobial effect can occur when article 30 comes into contact with an alcohol or water-based electrolyte, such as bodily fluids or body tissue in a patient's mouth, releasing metal ions such as, for example, Ag+, Al+, atoms, molecules, clusters, and the like. The concentration of metal required to produce an antimicrobial effect will vary depending on the metal in the metal oxide. In some examples, the antimicrobial effect can be achieved at a concentration of less than about 10 ppm in bodily fluids, such as saliva. In some examples, metal oxides within outer layer 34 may exhibit at least a 2-log microbial reduction against S. aureus and S. mutans after 24 hours of exposure. It may be determined by appropriate modification of the test method after testing in accordance with ISO test method ISO 22196:2011 "Measurement of antibacterial activity on plastics and other non-porous surfaces," Measure the log reduction to accommodate the test material. Additionally or alternatively, the metal oxide may prevent calculus from accumulating on the dental appliance, or may contain additives to prevent the formation of cavities in the patient's teeth.

4 is a schematic cross-sectional view of an example dental article 40 that includes a polymer-based substrate 12 having a multi-layer, water-resistant coating 42 comprising parylene. The multi-layer water resistant coating 42 includes an intermediate layer 26 on the polymer-based substrate 12 and a second layer 28 on the intermediate layer 26 in addition to the first layer 24 . In some such examples, the second layer 28 may include parylene and help smooth the outer surface of the interlayer 26 , improve the crack resistance of the interlayer 26 , or reduce the passage of other materials through the interlayer 26 The water vapor transmission rate or transmission rate. Both the intermediate layer 26 and the second layer 28 may include components similar to those described above with respect to FIG. 2 .

5 is a flowchart illustrating an example technique for forming the dental articles 10, 20, 30, 40 of FIGS. 1-4. For illustrative purposes, the technique of FIG. 5 is described in conjunction with various aspects of dental articles 10 , 20 , 30 , 40 . Such descriptions are not intended to be limiting, however, and the techniques of FIG. 5 may be used with other dental articles, or dental articles 10, 20, 30, 40 may be formed using other techniques than those described in FIG. 5 .

The technique of FIG. 5 includes forming a polymer-based substrate 12 (50) for a dental article 10, and coating the polymer-based substrate 12 (52) with a water-resistant coating 14, 22 comprising parylene. As described above, the dental article 10 may include a dental appliance, crown, night guard, retainer, implant, denture, partial, temporary replacement, elastic band, spring, constructed from the polymer-based substrate 12 , spring appliances, polymeric archwires and arcuate members, custom force members, accessories, stents and other bonded appliances, trays for delivering therapeutic agents, and the like.

In some examples, the polymer-based substrate 12 may comprise a polymer material having a defined elastic modulus greater than about 300 MPa. The relatively high elastic modulus of the polymer-based substrate 12 may allow the dental article 10 to exhibit a sufficient degree of strength and stiffness even when the polymer material remains relatively thin, which may be particularly useful for certain dental applications such as braces. In some examples, the polymer-based substrate 12 may comprise acrylate polymers, methacrylates, epoxies, polyesters, polyurethanes, polycarbonates, silicones, and the like. The polymer-based substrate 12 may be a thermoset polymer material or a thermoplastic polymer material. Suitable acrylate polymers may include urethane (meth)acrylate polymers. Such urethane acrylate polymers are particularly useful due to their mechanical properties in terms of body temperature and thermoformability. As discussed above, the elastic modulus of the polymer-based substrate 12 may decrease over time in the presence of water. Water can also accelerate the relaxation of stresses exerted by a flexed or strained polymer-based substrate.

The polymer-based substrate 12 may be formed using any suitable technique. In some examples, a thermoforming molding process may be used by heating a sheet of polymeric material used to form polymer-based substrate 12 on a patient's three-dimensional dental mold and vacuum forming the sheet to the surface of the dental mold. contour to shape the polymer-based substrate 12 into the shape of the patient's teeth. In other examples, the polymer-based substrate 12 may be formed via three-dimensional printing based on a digital three-dimensional representation of the patient's teeth.

In some examples, polymer-based substrate 12 may be further treated prior to coating the substrate with water-resistant coating 14 . Additional processing steps may include, for example, trimming and/or removing excess material from the substrate, drilling/cutting holes, channels, slits, etc. in the substrate, and debonding the polymer-based substrate 12 as part of the forming process. air, drying the polymer-based substrate 12 to remove residual moisture, and the like. In some examples, in order to remove residual moisture from the polymer-based substrate 12, the polymer-based substrate 12 may be placed in a desiccant for a period of time during which time the water-resistant coating 14, 22, 32, or 42 is applied. Residual moisture or other materials were previously drawn from the polymer-based substrate 12 . The polymer-based substrate 12 may also be dried at elevated temperature, or vacuum dried at elevated or ambient temperature, to evaporate moisture, other solvents, or other impurities from the substrate.

Additionally or alternatively, a desiccant (eg, a hygroscopic agent) may be incorporated directly onto or into the polymeric material used to form the polymer-based substrate 12 . In some examples, the polymer-based substrate 12 can be polished or otherwise mechanically manipulated to reduce or eliminate sharp corners or edges or to otherwise better conform to the patient's oral cavity. Various finishing techniques such as polishing can also be performed to improve the clarity and surface finish of the part. Additionally or alternatively, the polymer-based substrate 12 may be treated prior to coating with parylene, such as by plasma etching, sandblasting, or abrasive tumbling, to enhance adhesion between the two materials together.

聚对二甲苯-N、聚对二甲苯

或它们的组合。在一些示例中，耐水涂层14可包括至少一层聚对二甲苯-C。The polymer-based substrate 12 may be coated with a water-resistant coating 14 (52) comprising parylene. In some examples, the water-resistant coating 14 may include at least one layer consisting of parylene that substantially encapsulates the polymer-based substrate 12 . The layer comprising parylene may be deposited with a layer thickness of at least 5 μm, at least 15 μm or at least 25 μm. Various modifications to parylene coatings can be made, for example, by using halogenated monomers and/or incorporating additives to provide additional properties, such as from SCS Coatings (Clear Lake, WI). WI)) of the microscopic RESIST. In some examples, the parylene within the water resistant coating 14 may include one or more layers of parylene-C, parylene-D, parylene-F, parylene HT, SCS micro

Parylene-N, Parylene

or their combination. In some examples, the water resistant coating 14 may include at least one layer of parylene-C.

In some examples, the water-resistant coating 14 may be deposited on the polymer-based substrate 12 using a self-initiated chemical vapor deposition method, with para-xylene dimer as a starting component. For example, the polymer-based substrate 12 can be positioned in a vacuum deposition chamber that is evacuated to a pressure of about 0.1 Torr. The paraxylene dimer reactant can be heated to form monomeric paraxylene gas, which is introduced into the vacuum deposition chamber containing the polymer-based substrate 12 . The monomer gas is deposited and polymerized on the surface of the polymer-based substrate 12 to substantially encapsulate the substrate with parylene.

In some examples, the water-resistant coating 14 may be applied after the polymer-based substrate 12 has been fully formed. In other examples, the water-resistant coating 14 may be formed as part of the construction of the polymer-based substrate 12 . For example, FIG. 6 is an example flow diagram illustrating a technique for forming the polymer-based substrate 12 and applying the water-resistant coating 14 to the polymer-based substrate 12 in a co-current process. For clarity, Figure 6 is described with respect to the articles and layers shown in Figures 7A-7G. 7A-7G are schematic cross-sectional views of an example layer building method for forming a dental article encapsulated with a water-resistant coating comprising parylene.

The technique of FIG. 6 includes forming a physical model 80 ( 60 ) of the patient's dental anatomy using any suitable technique, and optionally coating the model 80 ( 62 ) with a release agent 81 such as polyvinyl alcohol. FIG. 7A shows a dental model 80 coated with a release agent 81 .

Next, a first coating 82 comprising parylene may be applied (eg, using CVD) to the mold 80 (64) using the techniques described herein. FIG. 7B shows the tooth model 80 with the first coating 82 and the release agent 81 applied to the model 80 . Once the first coating 82 is formed, a sheet 84 of polymer-based substrate material may be thermoformed over the first coating 82 (66), as shown in Figure 7C. The sheet of polymeric material is formed from the same material used to form the polymer-based substrate 12 .

The polymer sheet 84 may then be trimmed (68) to the appropriate size along trim lines 86 using, for example, a CNC 5-axis milling or laser cutting tool. Any excess material 88 of the thermoformed polymer sheet may optionally be removed. Figure 7D shows the polymer sheet 84 trimmed to the desired size. At this point in production, a polymer-based substrate (eg, trimmed polymer sheet 84 ) will be formed with a parylene-containing layer (eg, first coating 82 ) applied to one side of the substrate side, while both materials are still on the tooth model 80.

As shown in Figure 7E, a second coating 90 comprising parylene can then be applied to the exposed surface of the thermoformed and trimmed polymer sheet 84 (70). The second coating 90 of parylene may be combined with the first coating 82 to form a continuous layer of polymer sheet 84 encapsulating the parylene. Excess portions of second coating 90 and first coating 82 may then be trimmed (72) along trim line 92, as shown in FIG. 7F, to define the dental article from the polymer-based substrate (eg, a thermoforming polymer sheet 84) and the boundary of a single continuous layer 94 comprising parylene (eg, combined first coating 82 and second coating 90) formed on a polymer-based substrate. The dental article can then be separated from the dental model ( 74 ), eg, by soaking the article and model in warm water to dissolve the release agent 81 (if present). Figure 7G shows a completed dental article 96 with thermoformed polymer sheet 84 forming a polymer-based substrate, and encapsulant coating 94 forming a water resistant layer comprising parylene.

The technique of FIG. 6 may provide several advantages in the manufacture of dental articles 96 . For example, by constructing the dental article 96 in the manner described above, in addition to any differences established by the thickness of the release agent 81, the parylene-containing coating 82 (eg, inner surface) formed on the interior surface of the dental article 96 The surface refers to the portion of the article facing the patient's teeth) that will closely follow or simulate the contours of the dental model 80. In some examples, having the outer surface of the coating 82 follow or mimic the contours of the dental model 80 will ensure that the coating 82 on the inner surface of the dental article 96 does not adversely affect the fit of the dental article 96 on the patient's teeth Or intersect the space intended to be occupied by the patient's dental anatomy.

In contrast to alternative constructions, the dental article may be formed by thermoforming a sheet of polymer-based substrate 12 on a dental model 80, removing the thermoformed sheet, and then coating the thermoformed sheet with a water resistant coating 14 The water resistant coating comprises parylene on both the inner and outer surfaces of the thermoformed sheet. In such a configuration, however, the inner surface of the thermoformed sheet will follow or mimic the contours of the patient's dental anatomy. When a subsequent water-resistant coating is applied to the inner surface, the water-resistant coating can adversely affect the fit of the article by being effectively added to the inner surface of the dental article such that the inner surface no longer closely follows or mimics the patient's teeth dental anatomy. In some examples, the dimensions of the dental model 80 may be oversized to anticipate the expected thickness of the water-resistant coating 14 applied. For example, the dental model 80 may be sized (eg, physically offset via computer modeling and three-dimensional printing) such that a polymer sheet (eg, a polymer-based substrate thermoformed on the dental model 80 ) 12) The corresponding contoured surface of the patient's dental anatomy is offset from the expected or target thickness of the water resistant coating 14. However, in some examples, variability in coating thickness, especially with increasing thickness of the water resistant coating 14, can still adversely affect the fit of the resulting dental article. By forming the dental article 96 using the techniques described above with respect to FIG. 6, the inner coating 82 will not adversely affect the fit of the dental article 96, even if the inner coating 82 is relatively thick.

Returning to Figure 5, once the polymer-based substrate 12 is formed (50) and coated with the parylene-containing water-resistant coating 14, one or more optional coatings may be applied to the article. For example, the technique of FIG. 5 also includes any of coating the polymer-based substrate 12 ( 54 ) with the intermediate layer 26 and coating the polymer-based substrate 12 ( 56 ) with the second layer 28 comprising parylene. Choose a step.

As noted above, the intermediate layer 26 may be deposited on the first parylene layer 24 using any suitable technique including, for example, chemical vapor deposition, evaporative deposition, sputtering, atomic layer deposition, dip coating, spray coating, and the like, And may comprise a polymeric hard coat as described above, or may comprise any suitable inorganic material such as metals, metal alloys, metal oxides, ceramics, glasses, crystalline minerals, and the like. In some examples, the intermediate layer 26 may be a transparent and continuous film. In examples that do not include second layer 28, intermediate layer 26 may form an outer layer (eg, outer layer 34) of polymer-based substrate 12, and may include one or more layers (eg, among inorganic material layers) polymer hard coat on top).

In some examples, the technique of FIG. 5 may also include coating the polymer-based substrate 12 with a second layer 28 comprising parylene over the intermediate layer 26 ( 56 ) such that the intermediate layer 26 is located in the initial water resistant layer (eg, between the first layer 24 ) and the second layer 28 . In some such examples, the intermediate layer 26 may improve the durability and wear characteristics of the dental article 20 as compared to a water-resistant coating (eg, the dental article 10) that includes only a single layer with parylene. Such improved wear characteristics can be used in certain dental applications, such as dental crowns or night guards where the chewing or grinding of teeth is involved.

The second layer 28 comprising parylene may be deposited on the polymer-based substrate 12 and any layer below.

Example

Example 1 - Table 1 provides example polymer formulations that can be used to form polymer-based substrate 12. The polymer formulations shown in Table 1 were mixed in a glass jar and placed on a roller mixer to prepare a homogeneous mixture. The mixture was degassed by mixing in a planetary agitator at 2000 rpm under vacuum. The mixture was then poured into silicone dogbone molds (V molds, ASTM D638). The filled mold was placed between two glass plates and cured in a broad spectrum UV chamber for approximately 5 minutes. The test samples were demolded and cured in the chamber for an additional 5 minutes.

Table 1 :

*DESMA, as described in US Patent 8,329,776 to Hecht et al., which is incorporated herein by reference in its entirety.

Some of the polymer substrate test samples were then coated with a layer of parylene via chemical vapor deposition. Selected test samples are placed in a vacuum chamber that is evacuated to a pressure of about 0.1 Torr. The para-xylene dimer in solid form is then heated to generate monomeric para-xylene gas, which is introduced into the vacuum deposition chamber containing the test sample. When the monomer gas contacts the surface of the test sample, the gas polymerizes to form parylene C (eg, poly(paraxylylene) modified by substituting a chlorine atom for one of the aromatic hydrogens). This process was continued until a layer thickness of about 25 μm was obtained.

The parylene-coated polymeric base substrate (dog bone with V-shaped geometry according to ASTM D638-10) was then subjected to a water conditioning test and compared to an uncoated control sample. The water conditioning test involves immersion of the test sample in a phosphate buffered saline (PBS) solution at 37°C for 1 to 6 days. The test samples were then tested for mechanical properties at a rate of 5 mm/min using an Insight material testing system with a 5 kN load cell from MTS, MN, USA to determine tensile strength, grip Tensile modulus (based on grip movement rather than strain gauges) and grip position at sample fracture. The results are listed in Table 2 below.

Table 2.

Example 2 - Test samples of the polymer-based substrate of Example 1 were prepared and some were coated with a water resistant layer with parylene having a thickness of about 25 μm as described above. The other test samples were coated with an alternative and commercially available water resistant coating and their mechanical properties were tested after immersing the test samples in a phosphate buffered saline (PBS) solution at 37°C for 24 hours. The test observations are recorded in Table 3.

table 3.

Example 3 - Test samples of the polymer-based substrate of Example 1 were prepared and some were coated with a single layer of a water resistant layer of parylene. The parylene water resistant layer was tested for stain resistance compared to uncoated samples. The two test samples were placed in the coffee solution at 60 degrees Celsius overnight. The color parameters (L*, a*, b*) of each test sample were quantified using an X-Rite Color i7 spectrophotometer from Grand Rapids, MI, USA. The staining test results are shown in Table 4.

Table 4.

Clause 1: In one example, a dental article includes a substrate comprising a polymeric material, wherein the elastic modulus of the substrate decreases upon exposure to water, and a water-resistant coating on the substrate layer, wherein the water resistant coating comprises parylene.

Clause 2: In some of the examples of the dental article of Clause 1, the substrate comprises an acrylate polymer.

Clause 3: In some of the examples of the dental article of Clause 2, the substrate comprises a urethane (meth)acrylate polymer.

Clause 4: In some of the examples of the dental article of Clause 1, the substrate has a modulus of elasticity of greater than about 100 MPa in a substantially dry condition.

Clause 5: In some of the examples of the dental article according to Clause 1, the article includes a dental appliance, a dental crown, a night guard, a retainer, a dental implant, a denture, a partial, a temporary dental replacement, Elastic bands, springs, spring appliances, polymeric archwires, arcuate members, custom force members, attachments, stents, or trays for delivery of therapeutic agents.

Clause 6: In some of the examples of the dental article of Clause 5, the article comprises a dental appliance, a retainer, or a dental crown.

Clause 7: In some of the examples of the dental article of Clause 1, the water-resistant coating comprises a layer comprising parylene, wherein the layer comprising parylene is defined between about 5 micrometers (μm) and about thickness between 50μm.

Clause 8: In some of the examples of the dental article of Clause 7, the layer comprising parylene defines a thickness of at least about 25 μm.

Clause 9: In some of the examples of the dental article of Clause 1, wherein the substrate comprises a three-dimensionally printed substrate.

Clause 10: In some of the examples of the dental article of Clause 1, the water-resistant coating comprises a first layer comprising parylene on the substrate, an intermediate layer on the first layer layer (the intermediate layer comprising an inorganic material or a polymeric hard coat), and a third layer comprising parylene on the intermediate layer.

Clause 11: In some of the examples of the dental article of Clause 10, wherein the inorganic material comprises at least one of a metal, a metal alloy, a metal oxide, a metal salt, a ceramic, a glass, or a mineral.

Clause 12: In some of the examples of the dental article of Clause 1, the water-resistant coating comprises a first layer comprising parylene on the substrate and an outer layer on the first layer layer, the outer layer comprising an inorganic material or a polymer hard coat.

Clause 13: In some of the examples of the dental article of Clause 12, the outer layer comprises the polymeric hard coat, the water resistant coating further comprising between the first layer and the outer layer an intermediate layer in between, and the intermediate layer includes an inorganic material.

Clause 14: In some of the examples of the dental article of Clause 1, the water-resistant coating comprises an intermediate layer on the substrate, the intermediate layer comprising an inorganic material or a polymeric hard coat, and A layer comprising parylene on the intermediate layer.

Clause 15: In some of the examples of the dental article of Clause 1, the water-resistant coating comprises a layer comprising parylene, and wherein the layer comprising parylene comprises less than about 5% Porosity.

Clause 16: In some of the examples of the dental article of Clause 1, the water resistant coating comprises a layer comprising parylene, and wherein the layer comprising parylene is vapor deposited.

Clause 17: In some of the examples of the dental article of Clause 1, the dental article further comprises a desiccant.

Clause 18: In some of the examples of the dental article of Clause 17, the desiccant comprises at least one of silica gel, sodium aluminosilicate, zeolite, a hydrophilic polymer, or a hydrophilic clay.

Clause 19: In some of the examples of the dental article of Clause 17, the desiccant is located between the substrate and the water-resistant coating.

Clause 20: In some of the examples of the dental article of Clause 17, wherein the desiccant is incorporated into the substrate.

Clause 21: In some of the examples of the dental article of Clause 17, the desiccant is included on or in discrete regions of the substrate.

Clause 22: In some of the examples of the dental article of Clause 1, the parylene comprises parylene-C.

Clause 23: In some of the examples of the dental article of Clause 1, the substrate includes a first surface roughness, and the water-resistant coating includes a second surface roughness that is less than the first surface roughness Spend.

Clause 24: In some of the examples of the dental article of Clause 1, wherein the substrate defines a first coefficient of friction, and the water-resistant coating defines a second coefficient of friction that is less than the first coefficient of friction.

Clause 25: In some of the examples of the dental article of Clause 1, the water-resistant coating comprises a layer comprising parylene, wherein the thickness of the layer is greater than the thickness of the substrate .

Clause 26: In some of the examples of the dental article of Clause 1, the water-resistant coating does not intersect a space intended to be occupied by the patient's dental anatomy.

Clause 27: In some of the examples of the dental article of clause 26, the inner surface of the substrate is dimensioned such that the substrate corresponds to a corresponding surface of the dental anatomy of the patient Deviation from the expected thickness of the water resistant coating.

Clause 28: In some of the examples of the dental article of Clause 1, the substrate comprises a thermoset polymeric material.

Clause 29: In some of the examples of the dental article of Clause 1, the substrate comprises a thermoplastic polymer material.

Clause 30: In one example, a method includes forming a substrate for a dental article, wherein the elastic modulus of the substrate decreases upon exposure to water, and is coated with a water-resistant coating comprising parylene the substrate.

Clause 31: In some of the examples of the method of Clause 30, forming the substrate comprises forming a brace, a crown, a night sheath, a retainer, a dental implant, a denture, a partial, a temporary Dental replacements, elastic bands, springs, spring appliances, polymeric archwires, arcuate members, custom force members, accessories, brackets or trays for delivery of therapeutic agents.

Clause 32: In some of the examples of the method of Clause 30, the substrate has a modulus of elasticity greater than about 100 MPa in a substantially dry condition.

Clause 33: In some of the examples of the method of clause 30, forming the substrate comprises three-dimensionally printing the substrate.

Clause 34: In some of the examples of the method of clause 33, a surface of the water-resistant coating facing a portion of the patient's dental anatomy does not intersect a space intended to be occupied by the patient's corresponding dental anatomy.

Clause 35: In some of the examples of the method of clause 33, the substrate is dimensioned such that a surface of the substrate facing the patient's dental anatomy corresponds to the patient's dental anatomy The surface deviates from the expected thickness of the water resistant coating.

Clause 36: In some of the examples of the method of Clause 30, wherein forming the substrate comprises thermoforming the substrate on a three-dimensional model of a patient's dental anatomy.

Clause 37: In some of the examples of the method of clause 36, wherein the three-dimensional model of the dental anatomy of the patient is dimensioned such that the substrate faces the three-dimensional model The surface of the patient deviates from the expected thickness of the water resistant coating from the corresponding surface of the dental anatomy of the patient.

Clause 38: In some of the examples of the method of clause 36, a surface of the water-resistant coating facing a portion of the dental anatomy does not intersect a space intended to be occupied by a corresponding dental anatomy of the patient.

Clause 39: In some of the examples of the method of Clause 30, wherein coating the substrate with the water-resistant coating comprises chemically vapor depositing a layer comprising parylene on the substrate.

Clause 40: In some of the examples of the method of Clause 30, wherein coating the substrate with the water-resistant coating comprises depositing on the substrate a thickness between about 5 micrometers (μm) and about 50 μm A layer of inter-thickness containing parylene.

Clause 41: In some of the examples of the method of Clause 30, the thickness of the layer comprising parylene is at least about 25 μm.

Clause 42: In some of the examples of the method of Clause 30, wherein coating the substrate with the water-resistant coating comprises chemically vapor depositing a first layer comprising parylene on the substrate and an intermediate layer comprising an inorganic material or a polymeric hard coat is deposited on the first parylene layer.

Clause 43: In some of the examples of the method of clause 42, the method further comprises chemically vapor depositing a second layer comprising parylene on the intermediate layer.

Clause 44: In some of the examples of the method of Clause 42, the inorganic material includes at least one of a metal, a metal alloy, a metal oxide, a metal salt, a ceramic, a glass, or a mineral.

Clause 45: In some of the examples of the method of Clause 30, forming the substrate includes incorporating a desiccant on a surface of the substrate or into the substrate.

Clause 46: In one example, a dental article includes a three-dimensionally printed polymeric substrate and a water-resistant coating applied on the substrate, wherein the water-resistant coating includes a parylene layer.

Clause 47: In some of the examples of the dental article of Clause 46, the three-dimensionally printed polymeric substrate defines an elastic modulus greater than about 100 MPa.

Clause 48: In some of the examples of the dental article of clause 46, the three-dimensional printed polymeric substrate comprises a polymer selected from the group consisting of (meth)acrylate polymers, epoxy resins, polyurethanes, polyesters, poly Urethane-based polymer substrates of carbonates and siloxanes.

Clause 49: In some of the examples of the dental article of Clause 46, the article includes a dental appliance for aligning a patient's teeth, a retainer, or a crown.

Clause 50: In some of the examples of the dental article of Clause 46, the water-resistant coating comprises a first layer on the substrate comprising parylene, an inorganic on the first layer An inorganic layer of material and a third layer comprising parylene on the inorganic layer.

Clause 51: In some of the examples of the dental article of Clause 50, the inorganic material comprises at least one of a metal, a metal alloy, a metal oxide, a metal salt, a ceramic, a glass, or a mineral.

Clause 52: In some of the examples of the dental article of Clause 46, the dental article further comprises a desiccant.

Clause 53: In some of the examples of the dental article of Clause 46, wherein the desiccant is located between the three-dimensional printed polymer substrate and the water-resistant coating.

Clause 54: In some of the examples of the dental article of Clause 46, the desiccant is incorporated into the three-dimensional printed polymer substrate.

Clause 55: In some of the examples of the dental article of Clause 46, the three-dimensionally printed polymer substrate includes a surface that defines a plurality of contour lines that create an aliasing effect.

Clause 56: In some of the examples of the dental article of Clause 55, wherein the water-resistant coating reduces aliasing effects of the three-dimensionally printed polymer substrate.

Clause 57: In some of the examples of the dental article of Clause 46, the three-dimensionally printed polymeric substrate includes a first plurality of surface textures having a texture size of less than about 20 μm.

Clause 58: In some of the examples of the dental article of Clause 57, the water-resistant coating includes a second plurality of surface textures having a texture size that is less than the size of the first plurality of surface textures.

Clause 59: In some of the examples of the dental article of Clause 46, wherein the three-dimensionally printed polymer substrate comprises a first surface roughness, and the water-resistant coating comprises less than the first surface roughness degree of second surface roughness.

Clause 60: In some of the examples of the dental article of clause 46, the three-dimensional printed polymer substrate defines a first coefficient of friction, and the water-resistant coating defines a second coefficient of friction that is less than the first coefficient of friction Two coefficients of friction.

Clause 61: In some of the examples of the dental article of Clause 46, wherein a surface of the water-resistant coating facing a portion of the dental anatomy does not align with a space intended to be occupied by a corresponding dental anatomy of a patient intersect.

Clause 62: In one example, a method includes forming a model of a patient's dental anatomy, applying a first coating comprising parylene to the model, thermoforming polymerizing on the first coating a sheet of polymeric material, trimming the sheet of polymeric material to form a polymer-based substrate, applying a second coating comprising parylene to the exposed surface of the polymer-based substrate, trimming the the first coating and the second coating to define a dental article, the dental article comprising the polymer-based substrate, the first coating and the second coating, and the dental The article is separated from the model.

Clause 63: In some of the examples of the method of Clause 62, the method further comprises coating the mold with a release agent prior to applying the first coating comprising parylene to the mold Model.

Clause 64: In some of the examples of the method of Clause 63, the method further comprises dissolving the release agent prior to separating the dental article from the mold.

Clause 65: In some of the examples of the method of Clause 62, the polymer-based substrate has a modulus of elasticity greater than about 100 MPa in a substantially dry condition.

Various examples have been described. These and other examples are within the scope of the following claims.

Claims (16)

1. A dental article comprising: A polymeric substrate characterized by a decrease in elastic modulus upon contact with water; a first water-resistant coating comprising parylene, wherein the first water-resistant coating is in contact with the polymeric substrate; a coating comprising an inorganic material, a polymeric hard coat, or a combination thereof, wherein the coating is in contact with the first water-resistant coating; and A second water resistant coating comprising parylene, wherein the second water resistant coating is in contact with the coating comprising an inorganic material, a polymeric hard coat, or a combination thereof. 2. The dental article of claim 1, wherein the polymeric substrate comprises a polymeric material selected from the group consisting of acrylate polymers, thermoset polymers, thermoplastic polymers, and combinations thereof, wherein the modulus of elasticity under substantially dry conditions is greater than 100 MPa. 3. The dental article of claim 1, which is a brace, crown, night guard, retainer, dental implant, denture, partial, temporary dental replacement, elastic band, spring , spring appliances, polymeric archwires, arcuate members, custom force members, accessories, stents, or trays for delivering therapeutic agents. 4. The dental article of claim 1, wherein the inorganic material comprises metals, metal alloys, metal oxides, metal salts, ceramics, glasses, minerals, or combinations thereof. 5. The dental article of claim 1, further comprising a desiccant, wherein the desiccant is located between or incorporated into the substrate and the water resistant coating. 6. The dental article of claim 1, wherein the substrate further comprises a surface having a plurality of contour lines that create an aliasing effect, wherein the water resistant coating reduces the mixing of the substrate stacking effect. 7. A method for preparing a dental article according to any one of claims 1 to 6, the method comprising: forming a substrate comprising a polymeric material having a reduced modulus of elasticity when exposed to water; contacting the substrate with a first water-resistant coating comprising parylene; contacting the first water resistant coating with a coating comprising an inorganic material, a polymeric hard coat, or a combination thereof; and The coating is contacted with a second water resistant coating comprising parylene. 8. The method of claim 7, wherein the substrate is a dental brace, crown, night sheath, retainer, dental implant, denture, part, temporary dental replacement, elastic band, spring, Spring appliances, polymeric arch wires, arcuate members, custom force members, attachments, stents, or trays for delivery of therapeutic agents. 9. The method of claim 7, wherein the forming of the substrate comprises three-dimensional printing. 10. The method of claim 7, wherein contacting the substrate with the first water resistant coating comprises chemical vapor deposition. 11. The method of claim 7, wherein contacting the coating comprising an inorganic material, a polymeric hard coat, or a combination thereof with the second water resistant coating comprises chemical vapor deposition. 12. The method of claim 7, wherein the inorganic material comprises a metal, metal alloy, metal oxide, metal salt, ceramic, glass, or mineral, or a combination thereof. 13. The method of claim 7, further comprising: forming a model of the patient's dental anatomy; applying the first water resistant coating to the model; thermoforming a sheet of polymeric material on the first water resistant coating; trimming the sheet of polymeric material; applying the second water resistant coating; and The dental article is separated from the model. 14. A dental article comprising: 3D printed polymer substrates; a first water resistant coating comprising parylene; Coatings comprising inorganic materials, polymeric hard coats, or combinations thereof; and A second water resistant coating comprising parylene. 15. The dental article of claim 14, wherein the three-dimensionally printed polymer substrate comprises a surface defining a plurality of contour lines that produce aliasing effects, and wherein the first water resistant coating and the second One or more of the water resistant coatings reduce the aliasing effect of the three-dimensional printed polymer substrate. 16. The dental article of claim 14, the first water resistant coating is in contact with a three-dimensionally printed polymeric substrate, the coating comprising an inorganic material, a polymeric hard coat, or a combination thereof and the The first water-resistant coating is in contact, and the second water-resistant coating is in contact with the coating comprising an inorganic material, a polymeric hard coat, or a combination thereof.

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